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| United States Patent |
5,543,398
|
|
Monteleone
, et al.
|
August 6, 1996
|
Para-C.sub.5 alkyl-substituted ethoxycyclohexanes, organoleptic uses
thereof and processes for preparing same
Abstract
Described are compounds defined according to the structure:
##STR1##
wherein Z represents para cyclohexylene or para phenylene and wherein
R.sub.1, R.sub.2 and R.sub.3 are the same or different methyl or hydrogen;
and wherein R.sub.4 represents hydrogen, methyl or ethyl with the proviso
that the sum of the carbon atoms in R.sub.1, R.sub.2, R.sub.3 and R.sub.4
is 2. Also described are para-C.sub.5 alkyl-substituted ethoxycyclohexanes
defined according to the structure:
##STR2##
wherein R.sub.1, R.sub.2 and R.sub.3 represent the same or different
methyl or hydrogen; and wherein R.sub.4 represents hydrogen, methyl or
ethyl with the proviso that the sum of the carbon atoms in R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 is 2 and uses thereof in augmenting or
enhancing the aroma of perfume compositions, colognes and perfumed
articles including but not limited to solid or liquid anionic, cationic,
nonionic or zwitterionic detergents, fabric softener compositions, fabric
softener articles and hair preparations; as well as processes for
preparing said para-C.sub.5 alkyl-substituted ethoxycyclohexanes.
| Inventors:
|
Monteleone; Michael G. (Hazlet, NJ);
Weiss; Richard A. (Pine Brook, NJ);
Evans; Marc D. (South Orange, NJ);
Hanna; Marie R. (Keyport, NJ)
|
| Assignee:
|
International Flavors & Fragrances Inc. (New York, NY)
|
| Appl. No.:
|
522122 |
| Filed:
|
August 31, 1995 |
| Current U.S. Class: |
512/23; 568/579 |
| Intern'l Class: |
A61K 007/46 |
| Field of Search: |
512/23
568/579
|
References Cited
U.S. Patent Documents
| 5403805 | Apr., 1995 | Gubitosa et al. | 502/185.
|
| 5426216 | Jun., 1995 | Genet et al. | 562/450.
|
| 5462923 | Oct., 1995 | Monteleone et al. | 512/19.
|
| Foreign Patent Documents |
| 544110A1 | Jun., 1993 | EP | .
|
| 0616994 | Sep., 1994 | EP | .
|
Other References
BASF AG, abstract of published and examined Japanese Application No.
JP95/051523-B2, published in the Derwent Chemical Patents Index Alerting
Abstracts Bulletin, Section "E General Chemical", week 9527. (1993).
Becker, et al, Perfumer & Flavorist, vol. 15, Nov./Dec. 1990, entitled:
"The Relation of Structure and Odor in Substituted Cyclohexanols" (article
at pp. 29-33 and front cover).
Eliel and Krishnamurthy, Chemical Abstracts, vol. 63, 1965, 3011g (abstract
of J. Org. Chem. 30(3), pp. 848-854, 1965).
Faillebin, Beilstein E II 6: H7,3 (abstract of Ann. Chim. 4, 156-82, 410-96
(1925).
Kameoka, et al, Chemical Abstracts, vol. 108, 1988, No. 108:62302g
(abstract of Kameoka, et al, Nippon Nogei Kagaku Kaishi 1987, 61(9),
1119-21 (Japan).
|
Primary Examiner: Reamer; James H.
Attorney, Agent or Firm: Liberman; Arthur L.
Claims
What is claimed is:
1. At least one para-C.sub.5 alkyl-substituted ethoxycyclohexane defined
according to the structure:
##STR152##
wherein R.sub.1, R.sub.2 and R.sub.3 represent the same or different
methyl or hydrogen; and wherein R.sub.4 represents hydrogen, methyl or
ethyl with the proviso that the sum of the number of carbon atoms in
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is 2.
2. A compound defined according to claim 1 having the structure:
##STR153##
3. A compound defined according to claim 1 having the structure:
##STR154##
4. A compound defined according to claim 1 having the structure:
##STR155##
5. A perfume composition comprising a perfume base and intimately admixed
therewith an aroma imparting, augmenting or enhancing quantity of at least
one compound defined according to claim 1.
6. A perfumed article comprising a perfumed article base and intimately
admixed therewith an aroma imparting, augmenting or enhancing quantity of
at least one compound defined according to claim 1.
7. A perfumed polymer comprising a microporous polymer and contained within
the interstices thereof an aroma imparting, augmenting or enhancing
quantity of at least one compound defined according to claim 1.
8. A cologne comprising a water, ethanol and an aroma imparting, augmenting
or enhancing quantity of at least one compound defined according to claim
1.
9. A process for augmenting, enhancing or imparting an aroma to a
consumable material selected from the group consisting of perfume
compositions, perfumed articles and colognes comprising the step of
intimately admixing with said consumable material an aroma imparting,
augmenting or enhancing quantity of at least one compound defined
according to claim 1.
10. The process of claim 9 wherein the consumable material is a perfume
composition.
11. The process of claim 9 wherein the consumable material is a perfumed
article.
12. The process of claim 9 wherein the consumable material is a cologne.
13. The process of claim 9 wherein the consumable material is a perfumed
polymer.
Description
BACKGROUND OF THE INVENTION
The instant invention relates to para-C.sub.5 alkyl-substituted
ethoxycyclohexanes defined according to the structure:
##STR3##
wherein R.sub.1, R.sub.2 and R.sub.3 represent the same or different
methyl or hydrogen; and wherein R.sub.4 represents hydrogen, methyl or
ethyl with the proviso that the sum of the carbon atoms in R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 is 2 and uses of same in augmenting or
enhancing the aroma of perfume compositions, perfumed articles and
colognes.
There has been considerable work performed relating to substances which can
be used to impart (modify, augment or enhance) fragrances to (or in)
various consumable materials. These substances are used to diminish the
use of natural materials, some of which may be in short supply and to
provide more uniform properties in the finished product.
Long-lasting, intense, substantive green, fresh cut grass-like, citrus,
privet hedge (Ligustrum vulgare)-like, woody, floral, muguet, rose petal,
balsamic and tomato leaf aromas with green, ozoney, woody, floral, muguet,
rose, powdery, robusta coffee, dark cocoa, fruity, fatty-oily and tomato
leaf topnotes and linden blossom, cucumber and melon-like undertones are
highly desirable in several types of perfume compositions, perfumed
articles and colognes (e.g., fruity and floral fragrances).
Perfume uses of ethoxycycloalkyl derivatives are well known in the
literature. Thus, Arctander "Perfume and Flavor Chemicals (Aroma
Chemicals)", Volume I, published in 1969 by the author at Monograph No.
713 discloses the compound having the structure:
##STR4##
for use in perfumery. Arctander discloses that the compound having the
structure:
##STR5##
has a powerful, pungent-floral, deep-sweet, warm odor suggestive of
ylang-ylang, pandanus and other exotic flowers. Arctander indicates that
this compound is useful in perfume compositions of the heavy-floral type,
in artificial ylang-ylang and in various types of soap perfumes and in
general as a floralizer with considerable power. Arctander further states
that the compound having the structure:
##STR6##
has a "peculiar nut-like, or earthy undertone". Bielstein, Volume E II 6,
488, H6, System 530a, 522-523 (abstract of Le Brazidec, Bull. Soc. Chim.
France[4], 31, 263) discloses that the compound having the structure:
##STR7##
has an anisic aroma. The synthesis of this compound is disclosed by Le
Brazidec and is further disclosed by Dutton, et al, Canadian Journal of
Chemistry, 31 (1953), 1138, 1140. The structure:
##STR8##
wherein R is methyl is shown by Bielstein, Volume E IV6 at page 3288 and
is also disclosed at Chemical Abstracts, Volume 7, No. 2716h (abstract of
J. Elisha Mitchell Sci. Soc., Volume 66, 171-4 (1950)). The compound
having the structure:
##STR9##
is also disclosed in Schoot, et al, U.S. Pat. No. 2,996,514.
The compounds having the structures:
##STR10##
are indicated to be prepared by Chemical Abstracts, Volume 73, 1970,
66192c. The preparation of the compound having the structure:
##STR11##
is also shown to be prepared by Bielstein, Volume E IV 6 at page 3280,
Chemical Abstracts, 1961, 13386d (Zavgorodnii II) and Chemical Abstracts,
Volume 49 (1955), No. 8848z (Zavgorodnii I).
Furthermore, the compound having the structure:
##STR12##
is shown to be prepared by Zavgorodnii III at Chemical Abstracts, Volume
71 (1969), No. 3088m. the compound having the structure:
##STR13##
is shown to be prepared using the compound having the structure:
##STR14##
as a starting material according to the reaction:
##STR15##
by Bielstein, E III 6, H6, 548. The compound having the structure:
##STR16##
is shown to be prepared using as a starting material the compound having
the structure:
##STR17##
according to the reaction:
##STR18##
by Bielstein, E IV 6, page 3378 and by Dutton, et al, Canadian Journal of
Chemistry, 31 (1953), pages 1138, 1142.
The compound having the structure:
##STR19##
is shown to be prepared by Bielstein, E III 6, H6, 505-6, System No. 530,
abstract of Ipatieff, et al, Journal of American Soc., 60 (1938), 1161 and
Bert, Bull. Soc. Chim., 37, 1252-70 (1925).
Copending Application for U.S. patent Ser. No. 08/428,420 filed on Apr. 25,
1995, Monteleone, et al describes 1-oxo-substituted and unsubstituted
isobutyl-4-ethoxy-benzenes and mixtures thereof with bicyclopentadiene
derivatives for use in perfumery and further discloses methods for
preparing same. Said Application for U.S. patent, Ser. No. 08/428,420 is a
Divisional of Application for U.S. patent, Ser. No. 08/299,966 filed on
Sep. 2, 1994 (now U.S. Pat. No. 5,462,923 issued on Oct. 31, 1995) having
the same title. Both Ser. Nos. 08/299,966 and 08/428,420 disclose the
compounds having the structures:
##STR20##
for use in perfumery and further disclose that these compounds have
"long-lasting, intense, substantive green, woody, privet hedge (Ligustrum
vulgare)-like, floral, lilac, ozoney, fennel and anisic aromas with
fruity, fresh green, ozoney, fresh air, "ocean breeze" and anisic
topnotes".
Alkylcyclohexanols are known to be useful in the field of perfumery. Thus,
"VERTENEX.RTM." is an article of commerce marketed by International
Flavors & Fragrances Inc., said "VERTENEX.RTM." having the structure:
##STR21##
Furthermore, "VERTENEX.RTM. HIGH CIS" is also an article of commerce
marketed by International Flavors & Fragrances Inc., which has the
structure:
##STR22##
Furthermore, "ORIVONE" also an article of commerce marketed by
International Flavors & Fragrances Inc., has the structure:
##STR23##
Para alkylcyclohexylalkyl ethers are known in the prior art. Thus, Eliel,
et al, Chemical Abstracts, Volume 63, 1965, 3011g (abstract of J. Org.
Chem. 30(3), pages 848-854) discloses the compound having the structure:
##STR24##
Faillebin, Bielstein, Volume E II 6 at H7, No. 2, discloses the compound
having the structure:
##STR25##
(abstract of Faillebin, ANN. CHIM. 4, 156-82, 410-96 (1925)). Hiromu, et
al, Chemical Abstracts, Volume 108, 1988 at monograph No. 108:62302g,
discloses the compound having the structure:
##STR26##
as being a component of an essential oil obtained from the root of
Glycyrrhiza glabra (abstract of Nippon Nogei Kagaku Kashi 1987, 61(9),
pages 1119-21 (Japan)). However, the aroma of this material is not
disclosed nor is it indicated that the compound having the structure:
##STR27##
contributes any aroma to the essential oil named.
Thus, nothing in the prior art discloses the unexpected, unobvious and
advantageous organoleptic properties of the Para-C.sub.5 alkyl-substituted
ethoxycyclohexanes of our invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is the capillary GC profile for the crude mixture produced according
to the reaction of Example I(A) containing the compound having the
structure:
##STR28##
FIG. 2 is the NMR spectrum for the compound having the structure:
##STR29##
prepared according to Example I(A)
FIG. 3 is the capillary GC profile for the reaction product of Example I(B)
containing the compound having the structure:
##STR30##
FIG. 4 is the NMR spectrum for distillation fraction No. 7 of the
distillation of the reaction product of Example I(B) for the compound
having the structure:
##STR31##
FIG. 5 is the capillary GC profile for the reaction product of Example I(C)
containing the compounds having the structures:
##STR32##
FIG. 6 is the NMR spectrum for distillation fraction No. 8 of the
distillation of the reaction product of Example I(C) for the compound
having the structure:
##STR33##
FIG. 7(A) is the capillary GC profile for the crude reaction product of
Example II(A) containing the compound having the structure:
##STR34##
FIG. 7(B) is the NMR spectrum for the compound having the structure:
##STR35##
prepared according to Example II(A).
FIG. 8 is the capillary GC profile for the reaction product of Example
II(B) containing the compounds having the structures:
##STR36##
FIG. 9 is the NMR spectrum for distillation fraction No. 4 of the
distillation of the reaction product of Example II(B) for the compound
having the structure:
##STR37##
FIG. 9(A) is an enlargement of section "A" of the NMR spectrum of FIG. 9.
FIG. 9(B) is an enlargement of section "B" of the NMR spectrum of FIG. 9.
FIG. 10 is the capillary GC profile for the reaction product of Example
III(A) containing the compound having the structure:
##STR38##
FIG. 11 is the NMR spectrum for the compound having the structure:
##STR39##
prepared according to Example III(A).
FIG. 12 is the capillary GC profile for the product produced according to
Example III(B) containing the compound having the structure:
##STR40##
FIG. 13 is the NMR spectrum for the compound having the structure:
##STR41##
prepared according to Example III(B).
FIG. 14 is the capillary GC spectrum for the reaction product of Example
III(C) containing the compounds having the structures:
##STR42##
FIG. 15 is the NMR spectrum of distillation fraction No. 6 of the
distillation of the reaction product of Example III(C) for the compound
having the structure:
##STR43##
FIG. 16 is a partial side elevation view and partial sectional view of an
apparatus for forming polymer pellets containing at least one of the
para-C.sub.5 alkyl-substituted ethoxycyclohexanes of our invention.
FIG. 17 is a section taken along the line 17--17 of FIG. 16.
DETAILED DESCRIPTION OF THE DRAWINGS
Referring to FIG. 1, FIG. 1 is the capillary GC profile for the crude
reaction product of Example I(A) (conditions: SE-30 column programmed from
100.degree.-220.degree. C. at 8.degree. C. per minute). The peak indicated
by reference numeral 10 is the peak for the compound having the structure:
##STR44##
FIG. 3 is the capillary GC profile for the reaction product of Example
I(B). The peak indicated by reference numeral 30 is the peak for the
compound having the structure:
##STR45##
FIG. 5 is the capillary GC profile for the reaction product of Example
I(C). The peak indicated by reference numeral 51 is the peak for the
compound having the structure:
##STR46##
The peak indicated by reference numeral 52 is the peak for the compound
having the structure:
##STR47##
FIG. 7(A) is the capillary GC profile for the reaction product of Example
II(A). The peak indicated by reference numeral 70 is the peak for the
compound having the structure:
##STR48##
FIG. 8 is the capillary GC profile for the reaction product of Example
II(B). The peak indicated by reference numeral 80 is the peak for the
compound having the structure:
##STR49##
The peak indicated by reference numeral 81 is the peak for the compound
having the structure:
##STR50##
The peak indicated by reference numeral 82 is the peak for the compound
having the structure:
##STR51##
FIG. 10 is the capillary GC profile for the reaction product of Example
III(A). The peak indicated by reference numeral 100 is the peak for the
compound having the structure:
##STR52##
FIG. 12 is the capillary GC profile for the reaction product of Example
III(B). The peak indicated by reference numeral 120 is the peak for the
compound having the structure:
##STR53##
FIG. 14 is the capillary GC profile for the reaction product of Example
III(C). The peak indicated by reference numeral 140 is the peak for the
compound having the structure:
##STR54##
The peak indicated by reference numeral 141 is the peak for the compound
having the structure:
##STR55##
The peak indicated by reference numeral 142 is the peak for the compound
having the structure:
##STR56##
Referring to FIGS. 16 and 17, the apparatus used in producing polymeric
fragrances containing the para-C.sub.5 alkyl-substituted
ethoxycyclohexanes of our invention comprises a device for forming scented
polyolefin (for example) pellets, which comprises a vat or container 212
into which a mixture of polyolefin such as polyethylene and an aromatic
substance or scented material is placed (in this case at least one of the
para-C.sub.5 alkyl-substituted ethoxycyclohexanes of our invention).
The container is closed by an air-tight lid 228 and the air-tight lid 228
is clamped to the container 212 by bolts 265.
A stirrer 273 traverses the lid or cover 228 in an air-tight manner and is
rotated in a suitable manner.
Container 212 having heating coils 212A which are supplied with electric
current through cable 224 from a rheostat or control 216 is operated to
maintain a temperature inside the container 212 such that polyethylene or
other thermoplastic polymer in the container will be maintained in the
molten or liquid state. It has been found advantageous to employ a
colorless, odorless polymer (e.g., polyethylene) with viscosity ranging
between 180 and 220 Saybolt seconds and having a melting point in the
range of 200.degree.-280.degree. F. The heater 212A is operated to
maintain the upper portion of the container 212 within a temperature range
of from 250.degree.-350.degree. F. The bottom portion of the container is
heated by means of heating coils 212A heated through control 220 connected
thereto through a connecting wire 222 to maintain the lower portion of the
container within a temperature range of from 250.degree.-350.degree. F.
Thus, polymer (e.g., polyethylene) is added to container 212 and is heated
from 10-12 hours whereafter a scented aroma imparting material (at least
one of the para-C.sub.5 alkyl-substituted ethoxycyclohexanes of our
invention) is added quickly to the melt. The material must be compatible
with the polyolefin and forms a homogeneous liquid melt therewith. The
scented material is of a type for the particular aroma desired and
formulated specifically for the scenting purpose for which the polyolefin
will be employed.
Generally, about 5-30% by weight of the scented material (containing at
least one of the para-C.sub.5 alkyl-substituted ethoxycyclohexanes of our
invention) are added to the polyolefin.
After the scent imparting material (e.g., a composition containing at least
one of the para-C.sub.5 alkyl-substituted ethoxycyclohexanes of our
invention) is added to the container 212, the mixture is stirred for a few
minutes, for example, 5-15 minutes, and maintained within the temperature
range as indicated, supra, by means of heating coils 212A.
The controls 216 and 220 are connected, respectively, through cables 214
and 222, respectively, to heating coils 212A. The said controls 216 and
220 are also connected through cables 224 and 225, respectively, to a
suitable power supply of electric current for supplying the electric power
to the heating coils 212A for heating purposes.
Thereafter, the valve "V" is opened permitting the mass to flow outwardly
through conduit 218/232 having a multiplicity of orifices 234, adjacent to
the lower side thereof. The outer end of the conduit 218/232 is closed so
that the liquid polymer (e.g., polyolefin) and aroma imparting material
(e.g., at least one of the para-C.sub.5 alkyl-substituted
ethoxycyclohexanes of our invention) will continuously drop through
orifices 234 downwardly from conduit 232. During this time, the
temperature of the polymer (e.g., polyolefin) and scent imparting material
(e.g., a mixture containing at least one of the para-C.sub.5
alkyl-substituted ethoxycyclohexanes of our invention) is accurately
controlled so that a temperature in the range of from about
210.degree.-275.degree. F. will exist in the conduit 218/232. The
regulation of the temperature through controls 216 and 220 is essential in
order to insure temperature balance to provide for the continuous dropping
or dripping of molten polymer (e.g., polyethylene) and scenting material
(e.g., one or more of the para-C.sub.5 alkyl-substituted
ethoxycyclohexanes of our invention) mixture through the orifices 234 at a
rate which will insure the formation of droplets 236 which will fall
downwardly onto a moving conveyor belt 238 caused to run between conveyor
wheels 240 and 242 beneath the conduit 232.
When the droplets 236 fall onto the conveyor belt 238, they form pellets
244 which harden almost instantaneously and fall off the end of the
conveyor belt 238 into a container 245 and utilized in processes as
illustrated, infra.
A feature of this aspect of the process of our invention is the provision
for moistening the conveyor belt 238 to insure rapid formation of the
solid polymeric (e.g., polyolefin) scented pellets 244 without sticking to
the belt. The conveyor belt 238 is advantageously fabricated of a material
which will not normally stick to a melted plastic but a moistening means
248 insures a sufficiently cold temperature of the belt surface for an
adequate formation of the pellets 244. The adequate moistening means
comprises a container 250 which is continuously fed with water 254 to
maintain a level for moistening a sponge element 256 which bears against
the exterior of the conveyor belt 238.
THE INVENTION
The present invention provides para-C.sub.5 alkyl-substituted
ethoxycyclohexanes defined according to the structure:
##STR57##
wherein R.sub.1, R.sub.2 and R.sub.3 are the same or different methyl or
hydrogen; and wherein R.sub.4 represents hydrogen, methyl or ethyl with
the proviso that the sum of the number of carbon atoms in R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 is 2.
The compositions of matter of our invention produced according to the
processes of our invention are capable of augmenting, enhancing or
providing green, fresh cut grass-like, citrus, privet hedge (Ligustrum
vulgare)-like, woody, floral, muguet, rose petal, balsamic and tomato leaf
aromas with green, ozoney, woody, floral, muguet, rose, powdery, robusta
coffee, dark cocoa, fruity, fatty-oily and tomato leaf topnotes and linden
blossom, cucumber and melon-like undertones to perfume compositions,
colognes and perfumed articles (e.g., solid or liquid anionic, cationic,
nonionic or zwitterionic detergents, fabric softener articles, dryer-added
fabric softener articles, fabric softener compositions, cosmetic powders,
hair preparations, perfumed polymers and the like).
The substances of our invention are prepared in the alternative by (i)
reacting phenetole (ethoxybenzene) having the structure:
##STR58##
with an acyl derivative defined according to the structure:
##STR59##
according to the reaction:
##STR60##
then reducing the resulting ketone according to the reaction:
##STR61##
in the presence of an appropriate catalyst; and finally, reducing the
resulting para ethoxyalkylbenzene derivative according to the reaction:
##STR62##
also in the presence of an appropriate catalyst under appropriate reaction
conditions; or (ii) reacting an alkyl phenol having the structure:
##STR63##
with base having the structure:
M.sub.C.sub.P (OH.sup.-)
(or having the structure:
M.sub.C (OH).sub.P
in order to form a salt having the structure:
##STR64##
according to the reaction:
##STR65##
and then reacting the resulting salt having the structure:
##STR66##
with an ethoxylating reagent indicated by the symbol:
[Et]
according to the reaction:
##STR67##
under appropriate reaction conditions.
With respect to the reaction:
##STR68##
in the compound having the structure:
##STR69##
X.sub.1 is chloro, bromo or hydroxy; R.sub.3 is hydrogen or methyl and
R.sub.4 ' is ethyl or methyl with the proviso that the sum of the carbon
atoms in R.sub.3 and R.sub.4 ' is 2. Furthermore, with respect to the
reaction:
##STR70##
this reaction takes place in the presence of a Lewis acid catalyst having
the structure:
M.sub.A (X.sub.2).sub.N
or having the structure:
M.sub.B (X.sub.2).sub.N-K (OR).sub.K
in the presence of a solvent or in the absence of a solvent. The compound
having the structure:
M.sub.A (X.sub.2l ).sub.N
is a metal halide wherein M.sub.A is a metal such as boron, aluminum, iron,
tin or zinc. The halide X.sub.2 is chloro, bromo, iodo or fluoro. N is is
the valence of the metal M.sub.A. Examples of the compound or Lewis acid
catalyst having the structure:
M.sub.A (X.sub.2).sub.N
are boron trifluoride, aluminum trichloride, ferric chloride, stannic
chloride or zinc chloride. On the other hand, the catalyst useful in the
practice of our invention may be a complex such as boron trifluoride
etherate, to wit:
BF.sub.3 (C.sub.2 H.sub.5 OC.sub.2 H.sub.5).
Furthermore, the Lewis acid catalyst useful in the practice of our
invention may have the structure:
M.sub.B (X.sub.2).sub.N-K (OR).sub.K
wherein M.sub.B is a metal such as aluminum; wherein X.sub.2 is a halide
such as chloro; and R represents lower alkyl such as methyl, ethyl or
isopropyl. N is the valence of the metal M.sub.B and K represents the
number of alkoxy moieties wherein:
O<K<N
and wherein:
N.ltoreq.4.
As stated, supra, the reaction may take place in the presence of or absence
of a solvent. Examples of solvents are 2-nitropropane having the
structure:
##STR71##
(the most preferred solvent); nitromethane, hydrocarbons or chlorinated
hydrocarbons.
The temperature of reaction may be between about 0.degree. C. up to about
40.degree. C. with a preferred temperature range of from about 0.degree.
C. up to about 5.degree. C.
The preferred reactants of the genus:
##STR72##
are those where X.sub.1 is chloro due to economic reasons.
At the end of the reaction, the reaction mass is distilled in order to
yield substantially pure materials defined according to the structure:
##STR73##
wherein R.sub.3 represents hydrogen or methyl and R.sub.4 ' represents
ethyl or methyl with the proviso that the sum of the carbon atoms in
R.sub.3 and R.sub.4 ' is 2.
The compounds having the structure:
##STR74##
are then further reacted by means of reduction using hydrogen and an
appropriate hydrogenation catalyst according to the reaction:
##STR75##
The hydrogenation catalyst may be palladium on carbon, platinum,
palladium, Raney nickel or rhodium. A preferred catalyst is 1% palladium
on carbon. Copper chromite catalysts are also useful. This reaction takes
place at a temperature of between 105.degree. up to about 120.degree. C.
in a solvent, preferably isopropyl alcohol and at a pressure in the range
of from about 200 psig (pounds per square inch gauge) up to about 450 psig
with a preferred reaction pressure of 400 psig. Thus, examples of the
preferred reaction of this aspect of the process of our invention are as
follows:
##STR76##
The time of reaction of this first hydrogenation step is between 110 and
140 minutes. Furthermore, the reaction, to wit:
##STR77##
must take place in the presence of a proton source. Examples of a proton
source are FILTROL.RTM., an acid ion exchange composition; or phosphoric
acid or citric acid.
The compounds having the structure:
##STR78##
thus produced are recovered from the reaction mass and further
hydrogenated using 3% ruthenium on carbon catalysts at a temperature in
the range of from 110.degree. up to 145.degree. C. and at a pressure in
the range of from 400 up to 700 psig for a period of time of from 0.25 up
to 10 hours according to the reaction:
##STR79##
Preferred reactions are, more specifically, the reaction:
##STR80##
and the reaction:
##STR81##
With reference to the reaction sequence:
##STR82##
in the compound having the structure:
##STR83##
R.sub.1, R.sub.2 and R.sub.3 are the same or different and each represents
methyl or hydrogen; and R.sub.4 represents hydrogen, methyl or ethyl with
the proviso that the sum of the number of carbon atoms in R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 is 2. In the compound:
M.sub.C.sub.P (OH.sup.-)
also shown as:
M.sub.C (OH).sub.P,
M.sub.c represents an alkali metal such as sodium, potassium or lithium or
an alkaline earth metal such as calcium or magnesium. When M.sub.c
represents an alkali metal, P is 1 and when M.sub.c is an alkaline earth
metal, P is 2. Preferably, M.sub.c is sodium. Preferably, the ethoxylation
reagent is diethyl sulfate, although ethoxylation reagents such as ethyl
chloride, ethyl bromide and ethyl iodide are also useful ethoxylation
reagents.
Preferred reaction sequences concerning the foregoing reaction sequence
are:
##STR84##
An additional ethoxylation reagent is a mixture of ethyl alcohol and 93%
concentrated sulfuric acid with the ratio of the ethyl
alcohol:concentrated sulfuric acid being 50:50 (weight:weight).
With respect to the reaction:
##STR85##
or for that matter, the generic reaction:
##STR86##
this reaction takes place in the presence of a 3% ruthenium/carbon
catalyst at 110.degree.-145.degree. C.; a pressure of 400-700 psig and a
time of reaction of from 0.25 up to 10 hours.
Alternatively, other ruthenium-based hydrogenation catalysts may be used
and these ruthenium-based hydrogenation catalysts are disclosed and
claimed in U.S. Pat. No. 5,403,805 issued on Apr. 4, 1995, the
specification for which is incorporated herein by reference. Furthermore,
other ruthenium-based catalysts can be used, for example, those set forth
in U.S. Pat. No. 5,426,216 issued on Jun. 20, 1995, the specification for
which is incorporated by reference herein.
Palladium on carbon catalysts for the reaction:
##STR87##
useful in carrying out our invention are set forth in published European
Patent Application No. 616,994, published on Sep. 28, 1994.
With respect to the reaction:
##STR88##
as well as the reaction:
##STR89##
the conditions of the reaction dictate the nature of the resultant product
insofar as the isomers of the resulting product are concerned. Thus, the
ratio of "cis:trans" and the ratio of optical isomers obtained is a
function of the conditions of reaction. For example, the isomers of the
compound having the structure:
##STR90##
are as follows:
##STR91##
Isomers of the compound having the structure:
##STR92##
are as follows:
##STR93##
Isomers of the compound having the structure:
##STR94##
are as follows:
##STR95##
Each of the foregoing isomers has optical isomers thereof.
Thus, for example, in carrying out the reaction:
##STR96##
according to Example II(B) in the presence of a 3% ruthenium on carbon
catalyst when the reaction takes place at a temperature in the range of
110-.degree.120.degree. C. at a pressure of 600 psig for a period of time
of 6.5 hours in the presence of an isopropanol solvent, where the 3%
ruthenium on carbon catalyst:reactant having the structure:
##STR97##
is 0.03:1 and the ratio of solvent:reactant having the structure:
##STR98##
is 0.088, the weight ratio of reaction products having the structures:
##STR99##
is 85:10:5, respectively.
With respect to the etherification reaction:
##STR100##
this etherification reaction preferably takes place in the presence of a
"phase transfer reagent" such as ALIQUAT.RTM. 336 (trademark of the Henkel
Corporation of Minneapolis, Minn.), tricapryl methyl ammonium chloride
having the structure:
##STR101##
wherein R.sub.1 ", R.sub.2 " and R.sub.3 " represent capryl; X.sub.3
represents chloro; and R.sub.4 " is methyl. Other phase transfer reagents
may also be used wherein X represents chloro or bromo; R.sub.1 ', R.sub.2
" and R.sub.3 " are the same or different C.sub.6 -C.sub.10 alkyl and
R.sub.4 " represents C.sub.1 -C.sub.3 alkyl.
The etherification reaction may take place in the presence of a calcium
phenate catalyst having the structure:
##STR102##
in accordance with the procedure of the People's Republic of China Patent
No. 1,023,643 (PCT Patent Application No. 91 CN 108 407 assigned to the
China Petrochemical General Corporation having DERWENT Excession No.
93-101478/13.
The folowing Table I sets forth the perfumery properties of various
compositions of matter so useful in the perfumery of our invention.
TABLE I
______________________________________
Description
of Composition Perfumery Properties
______________________________________
##STR103## A green, citrus, ozoney, privet hedge (Ligustrum
vulgare)-like aroma.
prepared according to
Example I(C) distillation
fraction No. 8.
##STR104## A green (fresh cut grass-like), woody, floral (muguet),
balsamic aroma with green, ozoney, woody, floral (muguet)
topnotes and linden blossom, cucumber, melon-like
undertones.
prepared according to
Example II(B) bulked
distillation fraction
Nos. 6-14.
##STR105## A floral (rose petal), tomato leaf, green, muguet aroma
with powdery, floral (rose), green, muguet, robusta
coffee, dark cocoa, fruity, tomato leaf and fatty-oily
topnotes.
prepared according to
Example III(C) bulked
distillation fractions
Nos. 5-8
______________________________________
One or more of the para-C.sub.5 alkyl-substituted ethoxycyclohexanes
prepared in accordance with the process of our invention and one or more
auxiliary perfume ingredients including, for example, alcohols, aldehydes,
ketones, terpenic hydrocarbons, nitriles, esters, lactones, ethers other
than the ethers of our invention, natural essential oils and synthetic
essential oils may be admixed so that the combined odors of the individual
components produce a pleasant and desired fragrance, particularly and
preferably in the citrus, fruity and woody types of fragrances. Such
compositions usually contain:
(a) the main note or the "bouquet" or foundation stone of the composition;
(b) modifiers which round off and accompany the main note;
(c) fixatives which include odorous substances which lend a particular note
to the perfume throughout all stages of evaporation and substances which
retard evaporation; and
(d) topnotes which are usually low boiling, fresh smelling materials.
In perfume compositions, it is the individual components which contribute
their particular olfactory characteristics, however, the overall sensory
effect of the perfume compositions will be at least the sum total of the
effects of each of the ingredients. Thus, the para-C.sub.5
alkyl-substituted ethoxycyclohexanes of our invention produced in
accordance with the processes of our invention can be used to alter,
modify or enhance the aroma characteristics of a perfume composition, for
example, by utilizing or moderating the olfactory reaction contributed by
another ingredient in the composition. In the alternative, the
para-C.sub.5 alkyl-substituted ethoxycyclohexanes of our invention can be
used to formulate a perfume composition by themselves.
The amount of the para-C.sub.5 alkyl-substituted ethoxycyclohexanes
prepared in accordance with the processes of our invention which will be
effective in perfume compositions as well as in perfumed articles (e.g.,
anionic, cationic, nonionic or zwitterionic detergents, soaps, fabric
softener compositions, fabric softener articles and perfumed polymers) and
colognes depends upon many factors including the other ingredients, their
amounts and the effects which are desired. It has been found that perfume
compositions containing as little as 0.01% of the para-C.sub.5
alkyl-substituted ethoxycyclohexanes prepared in accordance with the
processes of our invention or even less (e.g., 0.005%) can be used to
impart, augment or enhance green, fresh cut grass-like, citrus, ozoney,
privet hedge (Ligustrum vulgare)like, woody, floral, muguet, rose petal,
balsamic and tomato leaf aromas with green, ozoney, woody, floral, muguet,
rose, powdery, robusta coffee, dark cocoa, fruity, fatty-oily and tomato
leaf topnotes and linden blossom, cucumber and melon-like undertones to
soaps, cosmetics, anionic, cationic, nonionic or zwitterionic detergents,
fabric softener articles, micorporous polymers, particularly acrylic
resins, polyethylenes and other products. The amount employed can range up
to 100% of the fragrance components and will depend on considerations of
cost, nature of the end product, the effect desired on the finished
product and the particular fragrance sought.
The para-C.sub.5 alkyl-substituted ethoxycyclohexanes of our invention
prepared in accordance with the processes of our invention are useful
(taken alone or together with other ingredients in perfume compositions)
as (an) olfactory component(s) in detergents and soaps, space odorants and
deodorants, perfumes, colognes, toilet water, bath preparations such as
creams, deodorants, hand lotions and sun screens; powders such as talcs,
dusting powders, face powders, microporous "perfumed" slow release
polymers and the like.
When used as (an) olfactory component(s) in perfumed articles, as little as
0.005% of the para-C.sub.5 alkyl-substituted ethoxycyclohexanes prepared
in accordance with the processes of our invention, will suffice to impart,
augment or enhance green, fresh cut grass-like, citrus, ozoney, privet
hedge (Ligustrum vulgare)-like, woody, floral, muguet, rose petal,
balsamic and tomato leaf aromas with green, ozoney, woody, floral, muguet,
rose, powdery, robusta coffee, dark cocoa, fruity, fatty-oily and tomato
leaf topnotes and linden blossom, cucumber and melon-like undertones.
Generally no more than 6% of the para-C.sub.5 alkyl-substituted
ethoxycyclohexanes of our invention based on the ultimate end product is
required in the perfumed article. Accordingly, the range of use of the
para-C.sub.5 alkyl-substituted ethoxycyclohexanes of our invention in
perfumed articles, per se, is from about 0.005% up to about 6% by weight
based on the perfumed-article.
In addition, the perfume composition or fragrance composition of our
invention can contain a vehicle or carrier for the para-C.sub.5
alkyl-substituted ethoxycyclohexanes prepared in accordance with the
processes of our invention. The vehicle can be a liquid such as a
non-toxic alcohol, e.g., ethyl alcohol; a non-toxic glycol, e.g.,
propylene glycol or dipropylene glycol or the like. The carrier can be an
absorbent solid such as a gum (e.g., gum arabic, guar gum or xanthan gum
or combinations thereof) or components for encapsulating the composition
(such as by coacervation) or using prepolymers such as urea-formaldehyde
prepolymers which are able to form a urea-formaldehyde polymer capsule
around a liquid perfume center.
It will thus be apparent that the para-C.sub.5 alkyl-substituted
ethoxycyclohexanes prepared in accordance with the processes of our
invention can be utilized to alter, modify or enhance sensory properties
particularly organoleptic properties such as fragrances of a wide variety
of consumable materials.
The following Examples I, II and III set forth means for preparing the
para-C.sub.5 alkyl-substituted ethoxycyclohexanes of our invention. The
examples including and following Example IV, infra, set forth
illustrations of organoleptic utilities of the para-C.sub.5
alkyl-substituted ethoxycyclohexanes of our invention.
All parts and percentages given herein are by weight unless otherwise
specified.
EXAMPLE I
PREPARATION OF ETHYL 4-PENTYLCYCLOHEXYL ETHER
EXAMPLE I(A)
Reaction:
##STR106##
Into a 2 liter reaction vessel equipped with stirrer, thermometer and
cooling coils are placed 450 ml of 1-nitropropane (NIPAR.RTM.). The
nitropropane is cooled to a temperature of 0.degree.-8.degree. C.
350 Grams of anhydrous aluminum chloride is slowly added to the
nitropropane.
Over a period of 0.25 hours, 290 grams of ethoxybenzene having the
structure:
##STR107##
is added to the reaction mass.
Over a 2 hour period, 300 grams of the compound having the structure:
##STR108##
is added to the reaction mass with stirring.
The reaction mass is then stirred for a period of 30 minutes at
0.degree.-8.degree. C. The resulting reaction mass is then quenched onto 1
liter of a mixture of ice and water.
The resulting product exists now in two phases: an organic phase and an
aqueous phase. The organic phase is separated from the aqueous phase and
the organic phase is washed with equal volumes, consecutively, of sodium
bicarbonate (saturated aqueous solution), water and saturated aqueous
sodium chloride. The organic phase is then dried over anhydrous magnesium
sulfate and filtered. The filtrate is then "rushed over" yielding 307
grams of product, distilled as follows:
______________________________________
Vapor Liquid Vacuum
Fraction Temperature Temperature
mm/Hg
Number (.degree.C.) (.degree.C.)
Pressure
______________________________________
1 21/76 21/76 100/3
3 131 133 1.6
3 156 200 2.4
______________________________________
EXAMPLE I(B)
Reaction:
##STR109##
Into a 1 liter autoclave equipped for high pressure are charged the
following materials:
255 grams of the compound having the structure:
##STR110##
prepared according to Example I(A), supra;
230 grams of isopropyl alcohol; and
3 grams of 1% palladium on carbon.
The autoclave is sealed and heated to a temperature of
115.degree.-120.degree. C. Hydrogen feed is commenced and the autoclave is
pressurized at 400 psig using hydrogen. The autoclave, with shaking, is
pressurized at 400 psig hydrogen for a period of 20 hours. At the end of
the 2 hour period, the autoclave temperature is raised to
120.degree.-125.degree. C. while maintaining the 400 psig pressure. The
temperature is maintained at 120.degree.-125.degree. C. for a period of 1
hour.
At the end of the 1 hour period, the hydrogen feed is ceased; the autoclave
is cooled, depressurized and opened. The resulting product is filtered and
the resulting filtrate is fractionally distilled yielding the following
fractions:
______________________________________
Vapor Liquid Vacuum
Fraction Temperature Temperature
mm/Hg
Number (.degree.C.) (.degree.C.)
Pressure
______________________________________
1 25/28 23/110 150/30
2 94 120 1
3 91 118 0.8
4 91 118 0.8
5 91 118 0.8
6 92 118 0.8
7 92 118 0.8
8 92 118 0.8
9 92 126 0.8
10 44 175 0.6
______________________________________
Fractions 5-9 were bulked. Fractions 5-9 are the compound having the
structure:
##STR111##
as confirmed by NMR, IR and mass spectral analyses.
EXAMPLE I(C)
Reaction:
##STR112##
Into a 500 cc autoclave is placed 125 grams of the compound having the
structure:
##STR113##
prepared according to Example I(B);
15 grams anhydrous isopropyl alcohol; and
4 grams of 3% ruthenium on carbon.
The autoclave is sealed and heated to 110.degree.-115.degree. C. and
pressurized with hydrogen to 400 psig hydrogen.
The autoclave with hydrogen feed is run for a period of 11 hours at
110.degree.-115.degree. C. at 400 psig.
At the end of the reaction, the autoclave is cooled and opened and the
contents are filtered. The isopropyl alcohol is stripped and the resulting
product is mixed with propionic anhydride (50 grams) and refluxed for a
period of 1.5 hours.
The resulting product is quenched with an equal volume of water and washed
with an equal volume of saturated sodium carbonate.
The resulting product is then fractionally distilled yielding the following
fractions:
______________________________________
Vapor Liquid Vacuum
Fraction Temperature Temperature
mm/Hg
Number (.degree.C.) (.degree.C.)
Pressure
______________________________________
1 21/33 23/100 120/4
2 88 118 4
3 106 118 4
4 107 118 4
5 107 118 4
6 105 118 4
7 104 120 4
8 104 120 4
9 106 124 4
10 105 126 4
11 105 128 4
12 107 132 4
13 106 140 4
14 95 140 0.8
______________________________________
Fraction 8 is the compound having the structure:
##STR114##
as confirmed by NMR, IR and mass spectral analyses.
EXAMPLE II
PREPARATION OF ETHYL 4-(1',1'-DIMETHYLPROPYL)CYCLOHEXYL ETHER EXAMPLE II(A)
Reactions:
##STR115##
Summary Reaction:
##STR116##
Into a 2 liter reaction vessel equipped with stirrer, thermometer, reflux
condenser and heating mantle are placed the following ingredients:
sodium hydroxide - 156 grams;
water - 468 grams; and
ALIQUAT.RTM. 336 - 25 grams.
The resulting mixture is heated to 45.degree. C.
Over a period of 1 hour, 500 grams of t-amylphenol having the structure:
##STR117##
is added to the reaction mass with stirring while maintaining the
temperature at 45.degree. C.
Over a period of 2 hours while maintaining the reaction mass at 45.degree.
C., diethyl sulfate having the structure:
##STR118##
is added to the reaction mass. The reaction mass is maintained at
45.degree. C. with stirring for an additional 3 hour period.
At the end of the 3 hour period, 500 grams of 25% aqueous sodium hydroxide
is added to the reaction mass and heated at 45.degree. C. for a period of
1 hour.
At the end of the 1 hour period, the reaction mass is cooled to room
temperature and the reaction mass now exists in two phases: an organic
phase and an aqueous phase. The organic phase is admixed with 50 ml of
toluene. The organic phase is then dried over anhydrous magnesium sulfate.
The resulting product is then admixed with 40 grams of propionic anhydride
and the resulting mixture is heated to 100.degree. C. and maintained at
100.degree. C. with stirring for a period of 0.5 hours. The resulting
product is then cooled to 60.degree. C. and admixed with 100 ml water. The
resulting product now exists in two phases: an organic phase and an
aqueous phase. The organic phase is separated from the aqueous phase and
the organic phase is washed, consecutively, with an equal volume of
saturated aqueous sodium chloride followed by saturated aqueous sodium
bicarbonate. The resulting product is dried over anhydrous magnesium
sulfate and fractionally distilled yielding the following fractions:
______________________________________
Vapor Liquid Vacuum
Fraction
Temperature
Temperature mm/Hg Reflux
Number (.degree.C.)
(.degree.C.)
Pressure
Ratio
______________________________________
1 20/85 20/105 0.8/0.8
4:1
2 84 103 0.67 9:1
3 84 104 0.59 9:1
4 84 103 0.56 9:1
5 84 103 0.55 9:1
6 83 104 0.55 9:1
7 83 104 0.53 9:1
8 83 104 0.53 9:1
9 86 104 1.1 9:1
10 83 101 0.7 9:1
11 88 104 1.03 9:1
12 88 104 1.06 9:1
13 89 105 1.07 9:1
14 88 107 1.06 4:1
15 89 116 1.07 4:1
______________________________________
The resulting product has the structure:
##STR119##
as confirmed NMR, IR and mass spectral analyses.
EXAMPLE II(B)
Reaction:
##STR120##
Into a 1 liter autoclave equipped with a hydrogen pressurization tube are
place the following materials:
295 grams of the compound having the structure:
##STR121##
8.8 grams 3% ruthenium on carbon; and
100 grams anhydrous isopropyl alcohol.
The autoclave is sealed and pressurized with hydrogen. The temperature of
the autoclave is raised to 110.degree.-120.degree. C. and pressurized at
600 psig with hydrogen. The hydrogen pressurization continues for a period
of 6.5 hours at a temperature of 110.degree.-120.degree. C.
At the end of the 6.5 hour period, the autoclave is cooled and opened and
the contents are filtered.
The resulting filtrate is distilled using a fractional distillation column
yielding the following fractions:
______________________________________
Vapor Liquid Vacuum
Fraction Temperature Temperature
mm/Hg
Number (.degree.C.) (.degree.C.)
Pressure
______________________________________
1 23/30 23/105 100/30
2 91 106 3
3 97 112 3
4 96 112 4
5 97 115 4
6 95 115 4
7 95 118 3.5
8 99 118 4.0
9 100 122 4.0
10 99 126 3.0
11 100 133 3.0
12 94 190 1.1
13 94 192 1.0
14 94 193 1.0
15 82 212 0.8
______________________________________
Fractions 6-14 are bulked. Fractions 6-14 consist of the compound having
the structure:
##STR122##
and a small quantity of the compound having the structure:
##STR123##
with the ratio of isomers being 85 parts by weight of the compound having
the structure:
##STR124##
10 parts by weight of the compound having the structure:
##STR125##
5 parts by weight of the compound having the structure:
##STR126##
EXAMPLE III
PREPARATION OF ETHYL 4-(3'-METHYLBUTYL)CYCLOHEXYL ETHER
EXAMPLE III(A)
Reaction:
##STR127##
Into a 2 liter reaction vessel equipped with stirrer, thermometer, reflux
condenser and cooling coils are placed 500 grams of 1-nitropropane
(NIPAR.RTM.). The 1-nitropropane is cooled to 0.degree. C.
Over a period of 1 hour while maintaining the temperature of the reaction
mixture at 0.degree.-10.degree. C., 496 grams of anhydrous aluminum
chloride is added to the reaction mass.
The reaction mass is cooled to 0.degree. C. and while maintaining the
reaction mass at 0.degree. C., over a period of 0.33 hours, 393 grams of
ethoxybenzene having the structure:
##STR128##
is added to the reaction mass.
While maintaining the reaction mass at 0.degree.-10.degree. C. over a
period of 1 hour, 425 grams of the compound having the structure:
##STR129##
is added to the reaction mass. The reaction mass is then stirred at
0.degree.-10.degree. C. for a period of 0.5 hours.
The reaction mass is then added to 1 liter of a mixture of ice and water.
The resulting mixture now exists in two phases: an organic phase and an
aqueous phase. The organic phase is separated from the aqueous phase and
dried over anhydrous magnesium sulfate. The resulting mixture is filtered
and the resulting product is distilled in a fractional distillation column
yielding the following fractions:
______________________________________
Vapor Liquid Vacuum
Fraction Temperature Temperature
mm/Hg
Number (.degree.C.) (.degree.C.)
Pressure
______________________________________
1 80/69 21/109 110/1
2 60 129 0.8
3 112 145 0.8
4 122 147 0.6
5 149 163 0.6
6 143/139 163/159 0.6
7 135 202 0.6
______________________________________
The resulting product has the structure:
##STR130##
as confirmed by NMR, IR and mass spectral analyses.
EXAMPLE III(B)
Reaction:
##STR131##
Into 1 liter autoclave equipped with hydrogen feed line are placed the
following ingredients:
438 grams of the compound having the structure:
##STR132##
prepared according to Example III(A);
85 grams anhydrous isopropyl alcohol; and
4 grams 1% palladium on carbon.
The autoclave is sealed and the contents are heated to
110.degree.-115.degree. C. Hydrogen is fed in keeping the pressure at 400
psig. The hydrogen feed continues for a period of 2.25 hours maintaining
the pressure at 400 psig and maintaining the temperature in the range of
115.degree.-128.degree. C. At the end of the 2.25 hour period, the
autoclave is cooled, depressurized and opened. The resulting mixture is
filtered. The filtrate is then fractionally distilled yielding the
following fractions:
______________________________________
Vapor Liquid Vacuum
Fraction Temperature Temperature
mm/Hg
Number (.degree.C.) (.degree.C.)
Pressure
______________________________________
1 23/82 23/114 150/1
2 86 114 1
3 87 114 1
4 89 115 1
5 91 118 1
6 93 116 1
7 96 120 1.5
8 91 116 1.0
9 91 116 1.0
10 90 116 1.0
11 90 116 1.2
12 90 116 1.0
13 89 116 1.0
14 89 116 1.0
15 45 135 1.0
16 30 200 0.5
______________________________________
Fractions 6-12 are bulked. The resulting product of which Fractions 6-12
consists has the structure:
##STR133##
EXAMPLE III(C)
Reaction:
##STR134##
Into a 1 liter autoclave equipped with hydrogen feed line are placed the
following ingredients:
200 grams (1.1 moles) of the compound having the structure:
##STR135##
prepared according to Example III(B);
150 grams anhydrous isopropyl alcohol; and
11.2 grams of 3% ruthenium on carbon.
The autoclave is sealed and the contents are heated to
115.degree.-120.degree. C. The autoclave is pressurized at 400 psig with
hydrogen and maintained at a temperature of 115.degree.-120.degree. C. at
400 psig hydrogen for a period of 2.5 hours. At the end of the 2.5 hour
period, the autoclave is cooled and opened and the contents are filtered.
The resulting filtrate is fractionally distilled on a fractional
distillation column yielding the following fractions:
______________________________________
Vapor Liquid Vacuum
Fraction Temperature Temperature
mm/Hg
Number (.degree.C.) (.degree.C.)
Pressure
______________________________________
1 23/33 23/100 150/60
2 90 102 2
3 92 100 2
4 92 100 2
5 89 97 1
6 87 98 1
7 85 100 0.6
8 81 101 0.6
9 82 104 0.5
______________________________________
Fractions 5-8 are bulked. Fractions 5-8 consist of the compound having the
structure:
##STR136##
contains 85% of the isomer having the structure:
##STR137##
and 15% by weight of the isomer having the structure:
##STR138##
("CIS":"TRANS"). The structures were confirmed by mass spectral, NMR and
IR analyses.
EXAMPLE IV
PERFUME FORMULATIONS
The following woody cologne perfume formulations are prepared:
______________________________________
Parts by Weight
Ingredients IV(A) IV(B) IV(C) IV(D)
______________________________________
Bergamot oil 150 150 150 150
Orange oil 200 200 200 200
Lemon oil 50 50 50 50
Eugenol 10 10 10 10
4-(4-methyl-4-hydroxy amyl-.DELTA..sup.3 -
40 40 40 40
cyclohexene) carboxaldehyde
(LYRAL .RTM. Trademark of
International Flavors &
Fragrances Inc. of New York,
New York)
Ylang oil 2 2 2 2
Petitgrain Paraguay
10 10 10 10
.gamma.-Methyl ionone
20 20 20 20
Vetiver Venezuela
18 18 18 18
3-.alpha.-Methyl-dodecahydro-6,6,
5 5 5 5
9a-trimethylnaptho[2,1-b]furan
Product produced by the
50 50 50 50
reaction of acetic anhydride,
polyphosphoric acid and 1,5,9-
trimethyl cyclododecatriene-
1,5,9 according to the process
of Example I of U.S. Letters
Pat. No. 3,718,697, the specifi-
cation for which is incor-
porated by reference herein.
Octahydro-9,9-dimethyl-1,6-
50 50 50 50
methanonaphthalene-1-[2H]-ol
produced according to
Example III of U.S. Letters
Pat. No. 3,996,169, the specifi-
cation for which is incorpor-
ated by reference herein.
The compound having the
12 0 0 0
structure:
##STR139##
produced according to
Example I(C), distillation
fraction No. 8.
The compound having the
0 12 0 0
structure:
##STR140##
produced according to
Example II(B), bulked
distillation fractions Nos. 6-14.
The compound having the
0 0 12 0
structure:
##STR141##
produced according to
Example III(C), bulked
distillation fractions Nos. 5-8.
The 30:30:40 (weight:weight:
0 0 0 12
weight) mixture of compounds
having the structures:
##STR142##
##STR143##
and
##STR144##
produced, respectively, accord-
ing to Examples I(C), II(B)
and III(C).
______________________________________
The compound having the structure:
##STR145##
imparts to this "woody cologne" formulation green, citrus, ozoney, privet
hedge (Ligustrum vulgare)-like undertones. Accordingly, the perfume of
Example IV(A) can be described as having:
a woody cologne aroma with green, citrus, ozoney, privet hedge (Ligustrum
vulgare)-like undertones.
The compound having the structure:
##STR146##
imparts to this woody cologne formulation green (fresh cut grass-like),
woody, floral (muguet), balsamic, linden blossom, cucumber and melon-like
undertones and green, ozoney, woody, floral (muguet) topnotes.
Accordingly, the perfume composition of Example IV(B) can be described as
having:
a woody cologne aroma with green (fresh cut grass-like), woody, floral
(muguet), balsamic, linden blossom, cucumber and melon-like undertones
with green, ozoney, woody and floral (muguet) topnotes.
The compound having the structure:
##STR147##
imparts to this woody cologne formulation floral (rose petal), tomato
leaf, green and muguet undertones with powdery, floral (rose), green,
muguet, robusta coffee, dark cocoa, fruity, tomato leaf and fatty-oily
topnotes. Accordingly, the perfume formulation of Example IV(C) can be
described as having:
a woody cologne aroma with floral (rose petal), tomato leaf, green, muguet
undertones and powdery, floral (rose), green, muguet, robusta coffee, dark
cocoa, fruity, tomato leaf and fatty-oily topnotes.
The mixture of compounds (30:30:40) having the structures:
##STR148##
can be described as having:
a woody cologne aroma with green, fresh cut grass-like, citrus, ozoney,
privet hedge (Ligustrum vulgare)-like, woody, floral, muguet, rose petal,
balsamic, tomato leaf, linden blossom, cucumber and melon-like undertones
with green, ozoney, woody, floral, muguet, rose, powdery, robusta coffee,
dark cocoa, fruity, fatty-oily and tomato leaf topnotes.
EXAMPLE V
PREPARATION OF COSMETIC POWDER COMPOSITION
Cosmetic powder compositions are prepared by mixing in a ball mill 100
grams of talcum powder with 0.25 grams of each of the substances set forth
in Table II below. Each of the cosmetic powder compositions has an
excellent aroma as described in Table II below:
TABLE II
______________________________________
Substance Aroma Description
______________________________________
##STR149## A green, citrus, ozoney, privet hedge (Ligustrum
vulgare)-like aroma.
prepared according to
Example I(C), distillation
fraction 8.
##STR150## A green (fresh cut grass-like), woody, floral (muguet),
balsamic aroma with green ozoney, woody, floral (muguet)
topnotes and linden blossom, cucumber and melon-like
undertones.
prepared according to
Example II(B), bulked
distillation fractions
6-14.
##STR151## A floral (rose petal), tomato leaf, green, muguet aroma
with powdery, floral (rose), green, muguet, robusta
coffee, dark cocoa, fruity, tomato leaf and fatty-oily
topnotes.
prepared according to
Example III(C), bulked
distillation fractions
5-8.
Perfume composition of
A woody cologne aroma with green,
Example IV(A). citrus, ozoney, privet hedge
(Ligustrum vulgare)-like
undertones.
Perfume composition of
A woody cologne aroma with green
Example IV(B). (fresh cut grass-like), woody,
floral (muguet), balsamic, linden
blossom, cucumber and melon-like
undertones with green, ozoney,
woody and floral (muguet)
topnotes.
Perfume composition of
A woody cologne aroma with floral
Example IV(C). (rose petal), tomato leaf, green,
muguet undertones and powdery,
floral (rose), green, muguet,
robusta coffee, dark cocoa,
fruity, tomato leaf and fatty-oily
topnotes.
Perfume composition of
A woody cologne aroma with green,
Example IV(D) fresh cut grass-like, citrus,
ozoney, privet hedge (Ligustrum
vulgare)-like, woody, floral,
muguet, rose petal, balsamic,
tomato leaf, linden blossom,
cucumber and melon-like undertones
with green, ozoney, woody, floral,
muguet, rose, powdery, robusta
coffee, dark cocoa, fruity, fatty-
oily and tomato leaf topnotes.
______________________________________
EXAMPLE VI
PERFUMED LIQUID DETERGENTS
Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonic
acid as more specifically described in U.S. Pat. No. 3,948,818 issued Apr.
6, 1976 and incorporated by reference herein) with aroma nuances as set
forth in Table II of Example V are prepared containing 0.10%, 0.15%,
0.20%, 0.30% and 0.35% of the substance set forth in Table II of Example
V. They are prepared by adding and homogeneously mixing the appropriate
quantity of substance set forth in Table II of Example V in the liquid
detergent. The detergents all possess excellent aromas as set forth in
Table II of Example V, the intensity increasing with greater
concentrations of substances as set forth in Table II of Example V.
EXAMPLE VII
PREPARATIONS OF COLOGNES AND HANDKERCHIEF PERFUMES
Compositions as set forth in Table II of Example V are incorporated into
colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and 5.0%
in 80%, 85%, 90% and 95% aqueous food grade ethanol solutions; and into
handkerchief perfumes at concentrations of 15%, 20%, 25% and 30% (in 80%,
85%, 90% and 95% aqueous food grade ethanol solutions). Distinctive and
definitive fragrances as set forth in Table II of Example V are imparted
to the colognes and to the handkerchief perfumes at all levels indicated.
EXAMPLE VIII
PREPARATION OF SOAP COMPOSITIONS
100 Grams of soap chips [per sample] (IVORY.RTM., produced by the Procter &
Gamble Company of Cincinnati, Ohio) are each mixed with 1 gram samples of
substances as set forth in Table II of Example V until homogeneous
compositions are obtained. In each of the cases, the homogeneous
compositions are heated under 8 atmospheres pressure at 180.degree. C. for
a period of 3 hours and the resulting liquids are placed into soap molds.
The resulting soap cakes, on cooling, manifest aromas as set forth in
Table II of Example V.
EXAMPLE IX
PREPARATION OF SOLID DETERGENT COMPOSITIONS
Detergents are prepared using the following ingredients according to
Example I of Canadian Patent No. 1,007,948 (incorporated by reference
herein):
______________________________________
Ingredient Percent by Weight
______________________________________
NEODOL .RTM. 45-11 (a C.sub.12 -C.sub.15 alcohol
12
ethoxylated with 11 moles of ethylene oxide)
Sodium carbonate 55
Sodium citrate 20
Sodium sulfate, water brighteners
q.s.
______________________________________
This detergent is a phosphate-free detergent. Samples of 100 grams each of
this detergent are admixed with 0.10, 0.15, 0.20 and 0.25 grams of each of
the substances as set forth in Table II of Example V. Each of the
detergent samples has an excellent aroma as indicated in Table II of
Example V.
EXAMPLE X
Utilizing the procedure of Example I at column 15 of U.S. Pat. No.
3,632,396 (the disclosure of which is incorporated herein by reference),
non-woven cloth substrates useful as drier-added fabric softening articles
of manufacture are prepared wherein the substrate, the substrate coating,
the outer coating and their perfuming material are as follows:
1. A water "dissolvable" paper ("Dissolvo Paper");
2. Adogen 448 (m.p. about 140.degree. F.) as the substrate coating; and
3. An outer coating having the following formulation (m. p. about
150.degree. F.):
57% C.sub.20-22 HAPS;
22% isopropyl alcohol;
20% antistatic agent; and
1% of one of the substances as set forth in Table II of Example V.
Fabric softening compositions prepared according to Example I at column 15
of U.S. Pat. No. 3,632,396 having the aroma characteristics as set forth
in Table II of Example V, supra, consist of a substrate coating having a
weight of about 3 grams per 100 square inches of substrate; a first
coating located directly on the substrate coating consisting of about 1.85
grams per 100 square inches of substrate; and an outer coating coated on
the first coating consisting of about 1.4 grams per 100 square inches of
substrate. One of the substances of Table II of Example V is admixed in
each case with the outer coating mixture, thereby providing a total
aromatized outer coating weight ratio to substrate of about 0.5:1 by
weight of the substrate. The aroma characteristics are imparted in a
pleasant manner to the head space in a dryer on operation thereof in each
case using said drier-added fabric softener non-woven fabrics and these
aroma characteristics are described in Table II of Example V, supra.
EXAMPLE XI
HAIR SPRAY FORMULATIONS
The following hair spray formulation is prepared by first dissolving PVP/VA
E-735 copolymer manufactured by the GAF Corporation of 140 West 51st
Street, New York, N.Y. in 91.62 grams of 95% of food grade ethanol. 8.0
Grams of the polymer is dissolved in the alcohol. The following
ingredients are added to the PVP/VA alcoholic solution:
______________________________________
Ingredient Percent by Weight
______________________________________
Dioctyl sebacate 0.05
Benzyl alcohol 0.10
Dow Corning 473 fluid (prepared by the
0.10
Dow Corning Corporation)
TWEEN .RTM. 20 surfactant (prepared by ICI
0.03
America Corporation)
One of the perfumery substances as set
0.10
forth in Table II of Example V, supra
______________________________________
The perfuming substances as set forth in Table II of Example V add aroma
characteristics as set forth in Table II of Example V which are rather
intense and aesthetically pleasing to the users of the soft-feel,
good-hold pump hair sprays.
EXAMPLE XII
CONDITIONING SHAMPOOS
Monamid CMA (prepared by the Mona Industries Company) (3.0 weight percent)
is melted with 2.0 weight percent coconut fatty acid (prepared by the
Procter & Gamble Company of Cincinnati, Ohio; 1.0 weight percent ethylene
glycol distearate (prepared by the Armak Corporation) and triethanolamine
(a product of the Union Carbide Corporation) (35.0 weight percent). The
resulting mixture is heated to 60.degree. C. and mixed until a clear
solution is obtained (at 60.degree. C.). This material is "COMPOSITION A".
GAFQUAT.RTM. 755N polymer (manufactured by the GAF Corporation of 140 West
51st Street, New York, N.Y.) (5.0 weight percent) is admixed with 0.1
weight percent sodium sulfite and 1.4 weight percent polyethylene glycol
6000 distearate produced by the Armak Corporation. This material is
"COMPOSITION B".
The resulting "COMPOSITION A" and "COMPOSITION B" are than mixed in a 50:50
weight ratio of A:B and cooled to 45.degree. C. and 0.3 weight percent of
perfuming substance as set forth in Table II of Example V is added to the
mixture. The resulting mixture is cooled to 40.degree. C. and blending is
carried out for an additional one hour in each case. At the end of this
blending period, the resulting material has a pleasant fragrance as
indicated in Table II of Example V.
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